A Novel Synthesis of Alkyl Chloroformate in the Gas Phase by Palladium-Catalyzed Reaction Using XCl (X = H or NO), CO, and Alkyl Nitrite

Abstract

Abstract A novel synthesis of chloroformate was developed by palladium-catalyzed reaction of XCl (X = H or NO), CO, and alkyl nitrite in the gas phase. When PdCl2/γ-Al2O3 or PdCl2/SiO2 was used as a catalyst, chloroformate was produced in good yield and with high selectivity. The reaction temperature had a strong influence on the formation rate of chloroformate, and its selectivity drastically depended on the nitrite/chloride ratio. When the nitrite/chloride ratio was less than 2, the selectivity of chloroformate was almost 100%. Dependence of the formation rate on the concentrations of CO and methyl nitrite was also examined.